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Description:

Single-molecule magnets represent promising materials due to their stable magnetic states and long relaxation times. Precise engineering of their quantum properties is of importance to realize advanced electronic devices, such as high-density data storage, quantum computing, and spintronics. Here, we investigate the spin state of nickelocene (NiCp2) and cobaltocene (CoCp2) molecules manipulated by Br atoms. With a combination of scanning tunneling microscopy and density functional theory calculations, we reveal that the high electronegativity of Br atoms significantly changes the magnetic properties of both NiCp2 and CoCp2. For NiCp2, the spin-state transition from its intrinsic S = 1 to S = 1/2 occurs when the Br atoms underlying the molecule consist of more than five atoms. The spin state is further shifted to S = 0 by approaching a Br-terminated tip toward the molecule. In contrast, a strong hybridization between CoCp2 and Br atoms leads to a complete quenching of its spin moment. This strategy for tuning molecular spin states provides a promising route toward the scalable design of molecular spintronic devices.

Rights:

• Creative Commons BY Attribution 4.0 International
  

Keyword: scanning tunneling microscopy, Single-molecule magnets, Spin-state transition, Nickelocene , Cobaltocene , density functional theory calculation

Date published: 2026-01-28

Publisher: American Chemical Society (ACS)

Journal:

• Journal of the American Chemical Society (ISSN: 00027863) vol. 148 issue. 3 p. 3356-3364

Funding:

• Japan Society for the Promotion of Science 24K21721
• Japan Society for the Promotion of Science 25H00422
• Academy of Finland 346824
• Academy of Finland 371709
• the European Union's Horizon Europe research and innovation programme under the Marie Sklodowska-Curie grant agreement 101207195
• Japan Society for the Promotion of Science 24KF0269

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1021/jacs.5c17873

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Updated at: 2026-02-08 08:30:04 +0900

Published on MDR: 2026-02-07 17:34:53 +0900